CA2048186A1 - Paper coating composition - Google Patents
Paper coating compositionInfo
- Publication number
- CA2048186A1 CA2048186A1 CA002048186A CA2048186A CA2048186A1 CA 2048186 A1 CA2048186 A1 CA 2048186A1 CA 002048186 A CA002048186 A CA 002048186A CA 2048186 A CA2048186 A CA 2048186A CA 2048186 A1 CA2048186 A1 CA 2048186A1
- Authority
- CA
- Canada
- Prior art keywords
- composition according
- water
- resin
- reaction
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
ABSTRACT OF THE DISCLOSURE
A paper coating composition which comprises:
(I) a pigment, (II) an aqueous binder, and (III) a resinous ingredient comprising (A) a water-soluble resin which is prepared by cross-linking (a) a condensation product of (a1) an alkylenediamine or a polyalkylenepolyamine and (a2) an urea compound with (b) a cross-linking compound. This composition imparts excellent ink receptivity, excellent water resistance, and in particular, excellent anti-blister property to paper.
A paper coating composition which comprises:
(I) a pigment, (II) an aqueous binder, and (III) a resinous ingredient comprising (A) a water-soluble resin which is prepared by cross-linking (a) a condensation product of (a1) an alkylenediamine or a polyalkylenepolyamine and (a2) an urea compound with (b) a cross-linking compound. This composition imparts excellent ink receptivity, excellent water resistance, and in particular, excellent anti-blister property to paper.
Description
PAPER COATING COMPOSII'ION
The present invention relates to a paper coating composition, and more particularly to a composition imparting excellent printing quality and excellent results of printing to paper.
The term "paper" as used herein should be interpreted in its broad sense and includes paper in the narrow sense as well as paperboard.
Coated paper obtained by applying a paper coating composition mainly composed of a pigment and an aqueous binder on paper, followed by necessary steps, such as drying and calendering, is widely used for commercial prints, magazines, books and the like due to its excellent properties such as printed results. With the increasing demand or higher quality and the development of high-speed printing techniques, constant efforts have ever been continued to further improve the coated paper quality. Particularly in the art of of~set printing predominating in various printing techniques, it is a weighty subject to add improvements in ink receptivity under the influence of damping water, water resistance such as wet pick or wet rub, and anti-blister property at a rotary press.
In order to resolve the above-described sub~ect, it is conventionally known to add to the paper coating composition a wet strength agent or printing quality improver including t~j melamine-formaldehyde resins, urea-formald~hyde resins, or polyamidepolyurea-formaldehyde resins, such as those disclosed in, fox example, JP-B-44-11667 and JP-B-S9-32597 (the tarm "JP-B" as used herein means an "examined published Japanese patent application (KOKOKU)").
Although these conventional wet strength agents or printing quality improvers exhibit effective characteristics, any of them has a serious defect or insufficiency in part of characteristics required and is not always satisfactory for practical use.
For example, aminoplast resins, e.g., melamine-formaldehyde resins and urea-formaldehyde resins, not only cause evolution of formaldehyde from the coating line or from the resulting coated paper but also produce substantially no effect on improving ink receptivi~y and anti-blister property. Bssides, as a pH of the coating composition increases, the water resistance improving effect by the aminoplast resins becomes less exerted. Polyamidepolyurea-formaldehyde resins are effectLve for impxoving not only water resistance but also ink receptivity and anti-blister property. The degree of improvements reached by them, however, is not necessarily sufficient against the recent demand for higher quality of coated paper. Efforts have hence been made to add further improvements. For example, an improved paper coating composition is proposed in EP~A-0220960. Nevertheless, there still has been a need for f~ 3 further enhanced perfQrmance to cope with the ever increasing demand for coated paper quality.
An object of the present invention is to provide a paper coating composition which endows paper with high water resistance and ink receptivity or the like, and in particular, excellent anti-blister property that has been hardly obtained by conventional techniques.
Other objects and effects of the present invention will be apparent from the following description.
The present inventors have conducted extensive investigation and, as a result, have found that a paper coating composition containing a specific water-soluble resin exhibits excellent performance and thus completed the present invention.
The present invention provides a paper coating composition which comprises:
(I) a pigment, (II) an aqueous binder, and (III) a resinous ingredient comprising (A) a water-soluble resin which is prepared by cross-linking (a~ a condensation product of (al) an alkylenediamine or a polyalkylenepolyamine and ~a2) an urea compowld with (b) a cross-linking compound.
~ r~
Resinous ingredient (III) according to the present invention may contain, in addition to water-soluble resin (A), (c) a polyalkylenepolyamine and/or (d) a reaction product of a polyaikylenepolyamine with a quaternarization agent. Polyalkylenepolyamine (c) and/ox the reaction product (d) will be hereunder referred to as "polyamine (B)".
Further, resinous ingredient (III) according to the present invention may be (C) a reaction product prepared from water-soluble resln (A) by further reacting with polyamine (B).
The present invention will be explained below in more detail.
Examples of alkylenediamine or polyalkylenepolyamine (al), which is one of the starting materials for water-soluble resin (A) used in the present invention, include aliphatic diamines such as ethylenediamine and propylene-diamine, and polyalkylenepolyamines such as diethylene-triamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine and 4,7-diaza-decane-1,10-diamine. Among them~ diethylenetriamine and triethylenetetramine are preferred from the industrial viewpoint. These alkylenediamines or polyalkylenepolyamines ~al) can be used either alone or in combina~ion of two or more thereof.
Examples of urea compound (a2), which is also a starting material for water-soluble resin (A) used in the present ~J ~
invention, include urea, thiourea, guanylurea, methylurea, dimethylurea and the like. Among them, urea is preferably used from the industrial viewpoint. These urea compounds (a2) can be used either alone or in combination of two or more thereof.
In the present invention, alkylenediamine or poly-alkylenepolyamine (al) and urea compound (a2) are subjected to a condensation reaction to produce condensation product (a), and thereafter condensation product (a) is further subjected to a cross-linking reaction with cross-linking compound (b) to produce water-soluble resin (A).
The condensation reaction between alkylenediamine or polyalkylenepolyamine (al) and urea compound (a2) is generally carried out at a temperature of from about lO0 to about 180C, and preferably from about 110 to about 160C, for a period of from about 1 to about 6 hours while driving ammonia produceA out o-f the reaction system (deammoniation).
Urea compound (a2) is preferably used in an amount of from 0.5 to 1 mol per mol of the primary and secondary amino groups of alkylenediamine or polyalkylenepolyamine (al). Tha reaction may be conducted in two-divided stages, in which a part of urea compound (a2) is reacted with alkylenediamine or polyalkylenepolyamine (al) at from 120 to 180C, and preferably from 140 ~o 160C, to conduct deammoniation, and then the re~t of urPa compound (a2) is added thereto and reacted at from 100 to 180C, and preferably from 110 to 160C, to complete the deammoniation.
The condensation product (a) thus obtained is further subjected to a cross-linking reaction with cross-linking compound (b) to produce water~soluble resin (A). Cross-linking compound (b) used herein is a compound capable of cross-linking condensation product (a) to make a resinous product, and examples thereof include:
(bl) aldehydes, (b2) epihalohydrins or a,~-dihalo-~-hydrins, (b3) reaction products of a urea compound (b3-1) with glyoxal (b3-2), and (b4) melamine-formaldehyde resins.
The cross-linking reaction between reaction product (a) and cross-linking compound (b) is preferably carried out in an aqueous solution having a total content of the components (a) and (b) of from about 20 to about 80% by weight, more preferably from about 30 to about 70% by weight. It is necessary to conduct this reaction under such a condition that cross-linking compound (b) reacts to achieve cross-linking of reaction product (a).
Cross-linking compounds (b) are individually explained hereunder.
Examples of aldehyde (bl) include formaldehyde;
alkylaldehydes, such as acetaldehyde and propionaldehyde;
glyoxal; and alkyldialdehydes, such as propanedial and butanedial; with formaldehyde and glyoxal being preferred for industrlal use. These aldehydes can be used either alone or in combination of two or more thereof.
The reaction between condensation product (a) and aldehyde (bl) is generally conducted under a cross-linking condition of a pH of 7 or below, preferably at a pH ranging from 3 to 6. The pH adjustment is preferably carried out by adding an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and the reaction is preferably conducted at a temperature of from about 40 to about 80C for a period of from about 1 to about 10 hours.
Alternatively, it is also preferred to conduct the reaction at first in an alkaline region of a pH ranging from 8 to 12, and thereafter to continue the reaction by adjusting the pH to an acidic region of 7 or below, more preferably to a range of 3 to 6. In this embodiment, the reaction under the alkaline condition is conducted at from about 40 to about 80C for from about 0.5 to about 5 hours, and the reaction under the acidic condition is conducted at from about 40 to about 80C for from about 1 to about 10 hours.
Aldehyde ~bl) is used preferably in such an amount that the aldehyde group is from about 0.1 to about 3 mols, more preferably from about 0.3 to about 1.5 mol, per mol of condensation product (a). After completion of the above-mentioned reaction, there is obtained an aqueous solution of water-soluble resin (A) to be used in the present invention.
If necessary, the pH of the reaction solution may be ad~usted in a range of from about 6 to about 10 by using an alkali, such as sodium hydroxide or po~assium hydroxide.
Epihalohydrins or rY,~-dihalo-~-hydrins (b2) are explained hereunder.
Epihalohydrin as cross-linking compound (b) is represented by formula:
CH~-CH(CH2)wX
wherein X rapresents a halogen atom, and w represents an integer of 1, 2 or 3.
a,~-Dihalo-~-hydrin as cross-linking compound (b) is represented by formula:
CH-Y
wherein X and Z each independently represent a halogen atom, and Y xepresents a hydroxyl group.
Preferred examples of the epihalohydrin include epichlorohydrin and epibromohydrin, and preferred examples o the a,~-dihalo-~-hydrin include 1,3-dichloro-2-propanol.
These epihalohydrins and ~,~-dihalo-~-hydrins can be used either alone or in combination of two or more thereof.
The reaction of condensation product (a) with epihalohydrin or a,~-dihalo-~-hydrin (b2) is preferably conducted under a condition o~ a pH of S or higher, more preferably at a pH ranging from 6 to 9, and at a temperature of from about 30 to about 90~C, more preferably from about 40 to about 80C, for from about 1 to about 10 hours.
Epihalohydrin or a,~-dihalo-~-hydrin (b2) is used preferably in an amount of from about 0.1 to about 3 mols, more preferably from about 0.3 to about 2 mols, per mol of condensation product (a).
Water-soluble resin (A) prepared by the reaction of the condensation product (a) with aldehyde (bl) or epihalohydrin or ~,~ dihalo-~-hydrin (b2) is obtained in the state of an aqueous solution, and preferably has a viscosity of from 50 to 1,000 cps at 25~C and a pH of from 6 to 10, each in an aqueous solution of 60% by weight.
Where reaction product (b3) of urea compound (b3-1) and glyoxal (b3-2) is used as cross-linking compound (b), examples of urea compound (b3-1) to be used therein include those exemplified hereinabove as component (a2). Reaction product (b3) can be obtained, as usually practiced, by admixing urea compound (b3-1) and ylyoxal (b3-2) in the presence of water. In this procedure, glyoxal (b3-2) is used preferably in an amount of from about 0.5 to about 5 mols per mol of urea compound (b3-1). Reaction product (b3) may be methylolized by the reaction with formaldehyde before or after urea compound ~b3-1) is allowed to react with glyoxal (b3-2). The methylolized product may be further converted to ~ '3~
an alkyl etherified product or a polyoxyalkylene ekherified product. Alternatively, there can also be used, for example, those polymerized with a monomer having an am.ide group, such as acrylamide or methacrylamide, before or after urea compound (b3-1) is allowed to react with glyoxal (b3-2); and those reacted with a polymer having an amide group, such as polyacrylamide or polymethacrylamide, after urea compound ~b3-1) is allowed to react with glyoxal (b3-2).
Such reaction product (b3) is further subjected to the cross-linking reaction with condensation product (a) to obtain water-soluble resin (A). Preferably, the aqueous solution containing condensation product (a) and reaction product (b3) is adjusted to a pH of 7 or below, more preferably to a pH ranging ~rom 1 to 5, by using an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and thereafter, the reaction is conducted at from about 40 to about 80C for about 1 to about 10 hours. After completion of the reaction, an aqueous solution of water-soluble resin ~A) to be used in the present invention is obtained, the pH of which may be adjusted, if necessary, in a range of from about 6 to about 10 by using an alkali, such as sodium hydroxide or potassium hydroxide.
Water-soluble resin (A) prepared by the reaction of condensation product (a) with reaction product (b3) is obtained in the state of an aqueous solution, and preferably ~ 3~
has a viscosity of from 50 to 1,000 cps at 25C and a pH of from 6 to 10, each in the aqueous sol.ution of 60% by weight.
Where melamine-formaldehyde resin (b4) is used as cross-linking compound (b), resin (b4) can be produced by known methods, for example, those disclosed in U.S. Patent ~,197,357.
Melamine-formaldehyde resin (b4) is subjected to the cross-linXing react.ion with condensation product (a) to obtain water-soluble resin (A). Preferably, the aqueous solution containing condensation product (a) and melamine-formaldehyde resin (b4) is adjusted to a pH of 7 or below, more preferably to a pH ranging from 2 to 6, by using an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and thereafter, the reaction is conducted at from about 40 to about 80C for from about 1 to about 10 hours. Melamine-formaldehyde resin (b4) is used preferably in an amount, based on the melamine nucleus, of from about 0.02 to about 2 mols, more preferably from about 0.1 to about 1 mol, per mol of condensation product (a).
After completion of the reaction, an aqueous solution of water-soluble resin (A) to be used in the present invention is obtained, the pH of which may be adjusted, if necessary, in the range of from about 6 to about lO by using an alkali, such as sodium hydroxide or potassium hydroxide. r~ater-soluble resin (A) prepared by the reaction of condensation product (a) with melamine-formaldehyde resin (b4) is obtained in the state of an aqueous solution, and preferably has a viscosity of from 50 to 1,000 cps at 25C and a pH of from 6 to 10, each in the aqueous solution of 60% by weight.
Water-soluble resin (A) prepared by any of ~he above-mentioned reactions can be used as resinous ingredient (III) of the paper coating composition according to the present invention. It is also possible to use two or more of -the cross-linking compounds (b) in the preparation of water-soluble resin (A).
For example, when cross-linking compound (b) is reaction product (b3) of urea compound (b3-1) with glyoxal (b3-2), water-soluble resin (A) prepared from condensation product (a) and reaction product (b3) may further react with at least one compound selected from aldehydes, epihalohydrins and ~,~-dihalo-~-hydrins to obtain another water-soluble resin (Al). Examples of these aldehydes, epihalohydrins and a,~-dihalo-~-hydrins are the same as those exemplified in the aforementioned components (bl) and (b2).
When water-soluble resin (A) is allowed to further react with aldehyde (bl), it is preferred to adjust the aqueous solution containing both reactants to a pH of 7 or below, more preferably to a pH ranging from 3 to 6, by using an acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and thereafter to conduct the reaction at from about 40 to about 80C for from about 1 to about 10 hours. Alternatively, it is also preferred to conduct the reaction at first in an alkaline region of a pH
ranging from 8 to 12, and then to continue the reaction by adjusting the pH to an acidic region of 7 or less, more preferably to a range of from 3 to 6. In the latter ca~e, the reaction under the alkaline condition is conducted at from about 40 to about 80C for from about 1 to about 10 hours. Aldehyde (bl) is used preferably in such an amount that the aldehyde group therein is from about 0.1 to about 3 mols per mol of water-soluble resin (A). After completion of the reac~ion, water-soluble resin (A1) to be used in the present invention is obtained, if necessary by adjusting a pH
in a range of from 6 to 10 with the use of an alkali such as sodium hydroxide or potassium hydroxide.
When water-soluble resin (A) prepared from alkylenedimine or polyalkylenepolyamine (a) and reaction product (b3) is allowed further to react with epihalohydrin or a,~-dihalo-~-hydrin (b2), it is preferred to conduct the reaction at a pH
of 5 or higher, more preferably at a pH of from 6 to 9, at a temperature of from about 30 to about 90C, more preferably from about 40 to about 80C, for a period of from about 1 to about 10 hours. Epihalohydrin or a,~-dihalo-~-hydrin (b2) is used preferably in an amount of from about 0.1 to about 3 mols per mol of water-soluble resin (A).
The aldehyde, epihalohydrin and ~,~-dihalo-~-hydrin to be used to obtain water-soluble re~in (Al) can be used either alone or in combination of two or more thereof. For example, IJ, ~3 ~
the aldehyde and the epihalohydrin may be used simultane-ously, and also the aldehyde and the ~,~-dihalo~-hydrin may be used simultaneously.
Water-soluble resin (A1) is obtained also in the state of an aqueous solution, and preferably has a viscosity of from 50 to 1,000 cps at 25C and a pH of from 6 to 10, each in an aqueous solution of 60% by weight.
Water-soluble resin (A) including resin (A1) is generally used in the state of an aqueous solution to prepare the paper coating composition according to the present invention, and as described above, the aqueous solution containing resin (~) in a concentration of 60% by weight has preferably a viscosity of from 50 to 1,000 cps at 25~C and a pH of from 6 to 10.
The paper coating composition according to the present invention comp~ises pigment (I), water-soluble binder (II), and resinous ingredient (III) containing water-soluble resin (A). Reslnous ingredient (III) may consist solely of water-soluble resin (A) or may further contain other components.
For example, resinous ingredient (III) may contain, in addition to water-soluble resin (A), polyamine (B) selected from (c) polyalkylenepolyamine and (d3 reaction product of a polyalkylenepolyamine with a ~uaternarization agent Further, water-soluble resin (A) in resinous ingredient (III) may be in the form of a reaction product with other components. For example, a reaction product ~C) obtained by ';j'! ~f~ ~ -3 reacting water-soluble resin (A) with polyamine (B) may be used as resinous ingredient (III).
Polyalkylenepolyamine (c), which is ~ se polyamine (B) or a starting compound of polyamine (B), is a compound having two primary amino groups and at least one secondary amino yroup per molecule. Specific examples of such compounds include diethylenetriamine, triethylenetetramine, tetra-ethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine, and 4,7-diazadecane-1,10-diamine.
Examples of quaternarization agents to be reacted with the polyalkylenepolyamine to prepare another polyamine (B) are shown below.
1) Halogen-containing compounds represented by formula:
Rl_x wherein Rl represents a lower alkyl group (e.g., having from 1 to about 6 car~on atoms), a lower alkenyl group (e.g., having from 2 to about 6 carbon atoms), a benzyl group, or a phenoxyethyl group; and X represents a halogen atom.
Preferred examples thereof include methyl chloride, ethyl chloride, propyl chloride, allyl chloride, benzyl chloride, phenoxyethyl chloride, and corresponding bromides or iodides.
The present invention relates to a paper coating composition, and more particularly to a composition imparting excellent printing quality and excellent results of printing to paper.
The term "paper" as used herein should be interpreted in its broad sense and includes paper in the narrow sense as well as paperboard.
Coated paper obtained by applying a paper coating composition mainly composed of a pigment and an aqueous binder on paper, followed by necessary steps, such as drying and calendering, is widely used for commercial prints, magazines, books and the like due to its excellent properties such as printed results. With the increasing demand or higher quality and the development of high-speed printing techniques, constant efforts have ever been continued to further improve the coated paper quality. Particularly in the art of of~set printing predominating in various printing techniques, it is a weighty subject to add improvements in ink receptivity under the influence of damping water, water resistance such as wet pick or wet rub, and anti-blister property at a rotary press.
In order to resolve the above-described sub~ect, it is conventionally known to add to the paper coating composition a wet strength agent or printing quality improver including t~j melamine-formaldehyde resins, urea-formald~hyde resins, or polyamidepolyurea-formaldehyde resins, such as those disclosed in, fox example, JP-B-44-11667 and JP-B-S9-32597 (the tarm "JP-B" as used herein means an "examined published Japanese patent application (KOKOKU)").
Although these conventional wet strength agents or printing quality improvers exhibit effective characteristics, any of them has a serious defect or insufficiency in part of characteristics required and is not always satisfactory for practical use.
For example, aminoplast resins, e.g., melamine-formaldehyde resins and urea-formaldehyde resins, not only cause evolution of formaldehyde from the coating line or from the resulting coated paper but also produce substantially no effect on improving ink receptivi~y and anti-blister property. Bssides, as a pH of the coating composition increases, the water resistance improving effect by the aminoplast resins becomes less exerted. Polyamidepolyurea-formaldehyde resins are effectLve for impxoving not only water resistance but also ink receptivity and anti-blister property. The degree of improvements reached by them, however, is not necessarily sufficient against the recent demand for higher quality of coated paper. Efforts have hence been made to add further improvements. For example, an improved paper coating composition is proposed in EP~A-0220960. Nevertheless, there still has been a need for f~ 3 further enhanced perfQrmance to cope with the ever increasing demand for coated paper quality.
An object of the present invention is to provide a paper coating composition which endows paper with high water resistance and ink receptivity or the like, and in particular, excellent anti-blister property that has been hardly obtained by conventional techniques.
Other objects and effects of the present invention will be apparent from the following description.
The present inventors have conducted extensive investigation and, as a result, have found that a paper coating composition containing a specific water-soluble resin exhibits excellent performance and thus completed the present invention.
The present invention provides a paper coating composition which comprises:
(I) a pigment, (II) an aqueous binder, and (III) a resinous ingredient comprising (A) a water-soluble resin which is prepared by cross-linking (a~ a condensation product of (al) an alkylenediamine or a polyalkylenepolyamine and ~a2) an urea compowld with (b) a cross-linking compound.
~ r~
Resinous ingredient (III) according to the present invention may contain, in addition to water-soluble resin (A), (c) a polyalkylenepolyamine and/or (d) a reaction product of a polyaikylenepolyamine with a quaternarization agent. Polyalkylenepolyamine (c) and/ox the reaction product (d) will be hereunder referred to as "polyamine (B)".
Further, resinous ingredient (III) according to the present invention may be (C) a reaction product prepared from water-soluble resln (A) by further reacting with polyamine (B).
The present invention will be explained below in more detail.
Examples of alkylenediamine or polyalkylenepolyamine (al), which is one of the starting materials for water-soluble resin (A) used in the present invention, include aliphatic diamines such as ethylenediamine and propylene-diamine, and polyalkylenepolyamines such as diethylene-triamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine and 4,7-diaza-decane-1,10-diamine. Among them~ diethylenetriamine and triethylenetetramine are preferred from the industrial viewpoint. These alkylenediamines or polyalkylenepolyamines ~al) can be used either alone or in combina~ion of two or more thereof.
Examples of urea compound (a2), which is also a starting material for water-soluble resin (A) used in the present ~J ~
invention, include urea, thiourea, guanylurea, methylurea, dimethylurea and the like. Among them, urea is preferably used from the industrial viewpoint. These urea compounds (a2) can be used either alone or in combination of two or more thereof.
In the present invention, alkylenediamine or poly-alkylenepolyamine (al) and urea compound (a2) are subjected to a condensation reaction to produce condensation product (a), and thereafter condensation product (a) is further subjected to a cross-linking reaction with cross-linking compound (b) to produce water-soluble resin (A).
The condensation reaction between alkylenediamine or polyalkylenepolyamine (al) and urea compound (a2) is generally carried out at a temperature of from about lO0 to about 180C, and preferably from about 110 to about 160C, for a period of from about 1 to about 6 hours while driving ammonia produceA out o-f the reaction system (deammoniation).
Urea compound (a2) is preferably used in an amount of from 0.5 to 1 mol per mol of the primary and secondary amino groups of alkylenediamine or polyalkylenepolyamine (al). Tha reaction may be conducted in two-divided stages, in which a part of urea compound (a2) is reacted with alkylenediamine or polyalkylenepolyamine (al) at from 120 to 180C, and preferably from 140 ~o 160C, to conduct deammoniation, and then the re~t of urPa compound (a2) is added thereto and reacted at from 100 to 180C, and preferably from 110 to 160C, to complete the deammoniation.
The condensation product (a) thus obtained is further subjected to a cross-linking reaction with cross-linking compound (b) to produce water~soluble resin (A). Cross-linking compound (b) used herein is a compound capable of cross-linking condensation product (a) to make a resinous product, and examples thereof include:
(bl) aldehydes, (b2) epihalohydrins or a,~-dihalo-~-hydrins, (b3) reaction products of a urea compound (b3-1) with glyoxal (b3-2), and (b4) melamine-formaldehyde resins.
The cross-linking reaction between reaction product (a) and cross-linking compound (b) is preferably carried out in an aqueous solution having a total content of the components (a) and (b) of from about 20 to about 80% by weight, more preferably from about 30 to about 70% by weight. It is necessary to conduct this reaction under such a condition that cross-linking compound (b) reacts to achieve cross-linking of reaction product (a).
Cross-linking compounds (b) are individually explained hereunder.
Examples of aldehyde (bl) include formaldehyde;
alkylaldehydes, such as acetaldehyde and propionaldehyde;
glyoxal; and alkyldialdehydes, such as propanedial and butanedial; with formaldehyde and glyoxal being preferred for industrlal use. These aldehydes can be used either alone or in combination of two or more thereof.
The reaction between condensation product (a) and aldehyde (bl) is generally conducted under a cross-linking condition of a pH of 7 or below, preferably at a pH ranging from 3 to 6. The pH adjustment is preferably carried out by adding an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and the reaction is preferably conducted at a temperature of from about 40 to about 80C for a period of from about 1 to about 10 hours.
Alternatively, it is also preferred to conduct the reaction at first in an alkaline region of a pH ranging from 8 to 12, and thereafter to continue the reaction by adjusting the pH to an acidic region of 7 or below, more preferably to a range of 3 to 6. In this embodiment, the reaction under the alkaline condition is conducted at from about 40 to about 80C for from about 0.5 to about 5 hours, and the reaction under the acidic condition is conducted at from about 40 to about 80C for from about 1 to about 10 hours.
Aldehyde ~bl) is used preferably in such an amount that the aldehyde group is from about 0.1 to about 3 mols, more preferably from about 0.3 to about 1.5 mol, per mol of condensation product (a). After completion of the above-mentioned reaction, there is obtained an aqueous solution of water-soluble resin (A) to be used in the present invention.
If necessary, the pH of the reaction solution may be ad~usted in a range of from about 6 to about 10 by using an alkali, such as sodium hydroxide or po~assium hydroxide.
Epihalohydrins or rY,~-dihalo-~-hydrins (b2) are explained hereunder.
Epihalohydrin as cross-linking compound (b) is represented by formula:
CH~-CH(CH2)wX
wherein X rapresents a halogen atom, and w represents an integer of 1, 2 or 3.
a,~-Dihalo-~-hydrin as cross-linking compound (b) is represented by formula:
CH-Y
wherein X and Z each independently represent a halogen atom, and Y xepresents a hydroxyl group.
Preferred examples of the epihalohydrin include epichlorohydrin and epibromohydrin, and preferred examples o the a,~-dihalo-~-hydrin include 1,3-dichloro-2-propanol.
These epihalohydrins and ~,~-dihalo-~-hydrins can be used either alone or in combination of two or more thereof.
The reaction of condensation product (a) with epihalohydrin or a,~-dihalo-~-hydrin (b2) is preferably conducted under a condition o~ a pH of S or higher, more preferably at a pH ranging from 6 to 9, and at a temperature of from about 30 to about 90~C, more preferably from about 40 to about 80C, for from about 1 to about 10 hours.
Epihalohydrin or a,~-dihalo-~-hydrin (b2) is used preferably in an amount of from about 0.1 to about 3 mols, more preferably from about 0.3 to about 2 mols, per mol of condensation product (a).
Water-soluble resin (A) prepared by the reaction of the condensation product (a) with aldehyde (bl) or epihalohydrin or ~,~ dihalo-~-hydrin (b2) is obtained in the state of an aqueous solution, and preferably has a viscosity of from 50 to 1,000 cps at 25~C and a pH of from 6 to 10, each in an aqueous solution of 60% by weight.
Where reaction product (b3) of urea compound (b3-1) and glyoxal (b3-2) is used as cross-linking compound (b), examples of urea compound (b3-1) to be used therein include those exemplified hereinabove as component (a2). Reaction product (b3) can be obtained, as usually practiced, by admixing urea compound (b3-1) and ylyoxal (b3-2) in the presence of water. In this procedure, glyoxal (b3-2) is used preferably in an amount of from about 0.5 to about 5 mols per mol of urea compound (b3-1). Reaction product (b3) may be methylolized by the reaction with formaldehyde before or after urea compound ~b3-1) is allowed to react with glyoxal (b3-2). The methylolized product may be further converted to ~ '3~
an alkyl etherified product or a polyoxyalkylene ekherified product. Alternatively, there can also be used, for example, those polymerized with a monomer having an am.ide group, such as acrylamide or methacrylamide, before or after urea compound (b3-1) is allowed to react with glyoxal (b3-2); and those reacted with a polymer having an amide group, such as polyacrylamide or polymethacrylamide, after urea compound ~b3-1) is allowed to react with glyoxal (b3-2).
Such reaction product (b3) is further subjected to the cross-linking reaction with condensation product (a) to obtain water-soluble resin (A). Preferably, the aqueous solution containing condensation product (a) and reaction product (b3) is adjusted to a pH of 7 or below, more preferably to a pH ranging ~rom 1 to 5, by using an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and thereafter, the reaction is conducted at from about 40 to about 80C for about 1 to about 10 hours. After completion of the reaction, an aqueous solution of water-soluble resin ~A) to be used in the present invention is obtained, the pH of which may be adjusted, if necessary, in a range of from about 6 to about 10 by using an alkali, such as sodium hydroxide or potassium hydroxide.
Water-soluble resin (A) prepared by the reaction of condensation product (a) with reaction product (b3) is obtained in the state of an aqueous solution, and preferably ~ 3~
has a viscosity of from 50 to 1,000 cps at 25C and a pH of from 6 to 10, each in the aqueous sol.ution of 60% by weight.
Where melamine-formaldehyde resin (b4) is used as cross-linking compound (b), resin (b4) can be produced by known methods, for example, those disclosed in U.S. Patent ~,197,357.
Melamine-formaldehyde resin (b4) is subjected to the cross-linXing react.ion with condensation product (a) to obtain water-soluble resin (A). Preferably, the aqueous solution containing condensation product (a) and melamine-formaldehyde resin (b4) is adjusted to a pH of 7 or below, more preferably to a pH ranging from 2 to 6, by using an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and thereafter, the reaction is conducted at from about 40 to about 80C for from about 1 to about 10 hours. Melamine-formaldehyde resin (b4) is used preferably in an amount, based on the melamine nucleus, of from about 0.02 to about 2 mols, more preferably from about 0.1 to about 1 mol, per mol of condensation product (a).
After completion of the reaction, an aqueous solution of water-soluble resin (A) to be used in the present invention is obtained, the pH of which may be adjusted, if necessary, in the range of from about 6 to about lO by using an alkali, such as sodium hydroxide or potassium hydroxide. r~ater-soluble resin (A) prepared by the reaction of condensation product (a) with melamine-formaldehyde resin (b4) is obtained in the state of an aqueous solution, and preferably has a viscosity of from 50 to 1,000 cps at 25C and a pH of from 6 to 10, each in the aqueous solution of 60% by weight.
Water-soluble resin (A) prepared by any of ~he above-mentioned reactions can be used as resinous ingredient (III) of the paper coating composition according to the present invention. It is also possible to use two or more of -the cross-linking compounds (b) in the preparation of water-soluble resin (A).
For example, when cross-linking compound (b) is reaction product (b3) of urea compound (b3-1) with glyoxal (b3-2), water-soluble resin (A) prepared from condensation product (a) and reaction product (b3) may further react with at least one compound selected from aldehydes, epihalohydrins and ~,~-dihalo-~-hydrins to obtain another water-soluble resin (Al). Examples of these aldehydes, epihalohydrins and a,~-dihalo-~-hydrins are the same as those exemplified in the aforementioned components (bl) and (b2).
When water-soluble resin (A) is allowed to further react with aldehyde (bl), it is preferred to adjust the aqueous solution containing both reactants to a pH of 7 or below, more preferably to a pH ranging from 3 to 6, by using an acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and thereafter to conduct the reaction at from about 40 to about 80C for from about 1 to about 10 hours. Alternatively, it is also preferred to conduct the reaction at first in an alkaline region of a pH
ranging from 8 to 12, and then to continue the reaction by adjusting the pH to an acidic region of 7 or less, more preferably to a range of from 3 to 6. In the latter ca~e, the reaction under the alkaline condition is conducted at from about 40 to about 80C for from about 1 to about 10 hours. Aldehyde (bl) is used preferably in such an amount that the aldehyde group therein is from about 0.1 to about 3 mols per mol of water-soluble resin (A). After completion of the reac~ion, water-soluble resin (A1) to be used in the present invention is obtained, if necessary by adjusting a pH
in a range of from 6 to 10 with the use of an alkali such as sodium hydroxide or potassium hydroxide.
When water-soluble resin (A) prepared from alkylenedimine or polyalkylenepolyamine (a) and reaction product (b3) is allowed further to react with epihalohydrin or a,~-dihalo-~-hydrin (b2), it is preferred to conduct the reaction at a pH
of 5 or higher, more preferably at a pH of from 6 to 9, at a temperature of from about 30 to about 90C, more preferably from about 40 to about 80C, for a period of from about 1 to about 10 hours. Epihalohydrin or a,~-dihalo-~-hydrin (b2) is used preferably in an amount of from about 0.1 to about 3 mols per mol of water-soluble resin (A).
The aldehyde, epihalohydrin and ~,~-dihalo-~-hydrin to be used to obtain water-soluble re~in (Al) can be used either alone or in combination of two or more thereof. For example, IJ, ~3 ~
the aldehyde and the epihalohydrin may be used simultane-ously, and also the aldehyde and the ~,~-dihalo~-hydrin may be used simultaneously.
Water-soluble resin (A1) is obtained also in the state of an aqueous solution, and preferably has a viscosity of from 50 to 1,000 cps at 25C and a pH of from 6 to 10, each in an aqueous solution of 60% by weight.
Water-soluble resin (A) including resin (A1) is generally used in the state of an aqueous solution to prepare the paper coating composition according to the present invention, and as described above, the aqueous solution containing resin (~) in a concentration of 60% by weight has preferably a viscosity of from 50 to 1,000 cps at 25~C and a pH of from 6 to 10.
The paper coating composition according to the present invention comp~ises pigment (I), water-soluble binder (II), and resinous ingredient (III) containing water-soluble resin (A). Reslnous ingredient (III) may consist solely of water-soluble resin (A) or may further contain other components.
For example, resinous ingredient (III) may contain, in addition to water-soluble resin (A), polyamine (B) selected from (c) polyalkylenepolyamine and (d3 reaction product of a polyalkylenepolyamine with a ~uaternarization agent Further, water-soluble resin (A) in resinous ingredient (III) may be in the form of a reaction product with other components. For example, a reaction product ~C) obtained by ';j'! ~f~ ~ -3 reacting water-soluble resin (A) with polyamine (B) may be used as resinous ingredient (III).
Polyalkylenepolyamine (c), which is ~ se polyamine (B) or a starting compound of polyamine (B), is a compound having two primary amino groups and at least one secondary amino yroup per molecule. Specific examples of such compounds include diethylenetriamine, triethylenetetramine, tetra-ethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine, and 4,7-diazadecane-1,10-diamine.
Examples of quaternarization agents to be reacted with the polyalkylenepolyamine to prepare another polyamine (B) are shown below.
1) Halogen-containing compounds represented by formula:
Rl_x wherein Rl represents a lower alkyl group (e.g., having from 1 to about 6 car~on atoms), a lower alkenyl group (e.g., having from 2 to about 6 carbon atoms), a benzyl group, or a phenoxyethyl group; and X represents a halogen atom.
Preferred examples thereof include methyl chloride, ethyl chloride, propyl chloride, allyl chloride, benzyl chloride, phenoxyethyl chloride, and corresponding bromides or iodides.
2) Dialkyl sulfites and dialkyl sulfates represented by formula:
( R20 ~ 2S V
wherein R2 represents ~ lower alkyl group (e.g., having from 1 to about 6 carbon atoms); and v represents an integer of 1 or 2.
Preferred examples thereof include dimethyl sulfate, diethyl sulfate, dimethyl sulfite and diethyl sulfite.
( R20 ~ 2S V
wherein R2 represents ~ lower alkyl group (e.g., having from 1 to about 6 carbon atoms); and v represents an integer of 1 or 2.
Preferred examples thereof include dimethyl sulfate, diethyl sulfate, dimethyl sulfite and diethyl sulfite.
3) Ethylene oxides represented by formula:
R3~cH-cH2 wherein R3 represents a hydrogen atom, a lower alkyl group (e.g., having from 1 to about 6 carbon atoms), a hydroxy-lower alkyl group (e.g., having from l to about 6 carbon atoms), or a phenyl group.
Preferred examples thereof include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and glycidol.
R3~cH-cH2 wherein R3 represents a hydrogen atom, a lower alkyl group (e.g., having from 1 to about 6 carbon atoms), a hydroxy-lower alkyl group (e.g., having from l to about 6 carbon atoms), or a phenyl group.
Preferred examples thereof include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and glycidol.
4) Epihalohydrins represented by formula:
CH2-CH(C~2)wx wherein X xepresents a halogen atom; and w represents an integer of l, 2 or 3.
Preferred examples thereof include epichlorohydrin and epibromohydrin.
~$~ s~3 5) Monohalohydrins represented by formula:
HOCHz(CH2)wx wherein X represents a halogen atom, and w represents an integer of 1, 2 or 3.
Preferred examples thereof include ethylenechlorohydrin and ethylenebromohydrin.
CH2-CH(C~2)wx wherein X xepresents a halogen atom; and w represents an integer of l, 2 or 3.
Preferred examples thereof include epichlorohydrin and epibromohydrin.
~$~ s~3 5) Monohalohydrins represented by formula:
HOCHz(CH2)wx wherein X represents a halogen atom, and w represents an integer of 1, 2 or 3.
Preferred examples thereof include ethylenechlorohydrin and ethylenebromohydrin.
6) Dihalohydrins represented by formula:
CH-Y
CH2- z wherein X represents a halogen atom, and either one of Y and Z represents a halogen atom and the other represents a hydroxyl group.
Preferred examples thereof include 1,3-dichloro-2-propanol and 2,3-dichloro-l~propanol.
Particularly preferred of these quaternarization agents is epichlorohydrin. The quaternarization a~ents may be used either individually or in combination of two or more thereof.
Polyamine (B) may be either one or both of polyalXylene-polyamine (c) and reaction product (d) between polyalkylene-polyamine (c) and the quaternarization agent.
- 17 ~
-` h~ ? ~L ~
Pigments which can be used as component (I) in the present invention include white inoxganic pigments, e.g., kaolin, talc, calcium carbonate (either ground or precipitated), aluminum hydroxide, satin whit~ and titanium oxide; and white organic synthetic pigments, e.g., polystyrene, melamine-formaldehyde resins, and urea-formaldehyde resins. They may be used either individually or in combination of two or more thereof. Organic or inorganic colored pigments may ~lso be used in combination.
Aqueous binders which can be used in the present invention as component (II) includes water-soluble binders and aqueous emulsion type binders. Examples of the water-soluble binders include modified or unmodified starches such as oxidized starch and phosphate-esterified starch, polyvinyl alcohol, water-soluble proteins such as casein and gelatin, and modifled cellulose such as carboxymethyl-cellulose.
Examples of the aqueous emulsion type binders include styrene-butadiene type resins, vinyl acetate xesins, ethylene-vinyl acetate resins, and methyl methacrylate-based resins. These aqueous binders may be used either ind;vidually or in combination of two or more thereof.
In the paper coating composition according to the present invention, resinous ingredient (III) is used preferably in an amount of from 0.05 to 5 parts by weight, more preferably from 0.1 to 2 parts by weight, per 100 parts by weight of pigment (I). The amount of resinous ingredient (III) ~ 18 ~
referred to herein is applicable to any of cases where the resinous ingredient (III) comprises water-soluble resin (A) alone, where it comprises both water-soluble resin (~) and polyamine (B), and where it comprises reaction product (C) prepared by further reacting water-soluble resin (A) with polyamine (B).
Aqueous binder (II) per se is conventionally used as a component for paper coating compositions, and its amount in the composition can vary in accordance with the usage of the composition. Aqueous binder (II) contained in the paper coating composition of the present invention is preferably in an amount of from 5 to 200 parts by weight, more preferably from 10 to 50 parts by weight, per 100 parts by weight of pigment (I).
The paper coating composition of the present invention preferably has a solids content ranging from about 20 to about 75% by weight based on the weight of the composition, but the solid content can vary depending on the kind of a coater, the usage of the composition and the like.
In the prepaxation of the paper coating composi.tion of the present invention, while resinous ingredient (III) is usually admixed ~ith the pigment and aqueous binder at the preparation of the composition, the effects of the present invention can be achieved as well by previously admixing resinous ingredient (III~ with either a piyment slurry or an ~,J ~ r., aqueous binder and then incorporating the mixture with other components.
If desired, the paper coating composition of the present invention may further contain other components, such as dispersing agents, viscosity or fluidity regulators, defoaming agents, antiseptics, lubricants, water retaining agents, and colorants including dyes and colored pigments.
The paper coating composition of the present invention can be applied on a paper su~strate by any of known coating means, such as blade coater, air knife coater, bar coater, size press coater, gate roll coater, and cast coater After coating, the paper is subjected to drying as required. If desired, the coated paper is subjected to a surface smoothening treatment by use of a supercalender, etc.
Coated paper obtained by using the paper coating composition according to the present invention exhibits various excellent properties. For example, it is excellent in ink receptivity and water resistance, and is particularly excellent in anti-blister property. Further, it is completely or substantially free from evolution of formaldehyde odor.
The present invention is now illustrated in greater detail with reference to Reference Examples and Examples, but it should be understood that the present invention is not deemed to be limited thereto. All the percents, parts and ratios are ~y weight unless otherwise indicated. In the _ 20 ~
3 ~, ~
Reference Examples and Examples, viscosities ~ere measured at 25C.
REFERENCE EX~MPLE 1 In a four-necked flask equipped with a thermometer, a reflux condens~r, and a stirring rod were charged 146.2 g (1.0 mol) of triethylenetetramine and 180.2 g ~3.0 mol) of urea, and the mixture was heated at an inner temperature of 120 - 140C for 2 hours to effect deammoniation. Thereafter, 150.4 g of water was added thereto to prepare an aqueous resin solution. To the solution was added 56.8 g (0.7 mol) of 37% formalin, and the mixture was allowed to react at 70C
for 4 hours. The reaction system was adjusted to pH 4.0 with 70% sulfuric acid, and the reaction was further continued at 70C for an additional period of 4 hours. The reaction mixture was adjusted to pH 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution Rl having a resin content of 60% and a viscosity of 350 cps.
In the same apparatus as used in Reference Example 1 were charged 146.2 g (1.0 mol) of triethylenetetramine and 60.1 g tl.0 mol) of urea, and the mixture was heated at an inner temperature of 140 - 160C for 3 hours to effect deammoniation. After cooling to 120C, 120.1 g (2.0 mol) of urea was added to the reaction mixture, followed by heating at an inner temperature of 120 - 130C for 2 hours to conduct deammoniation. Then, 134.9 g of water was added thereto to prepare an aqueous resin solution. To the solution was added 81.2 g ~1.0 mol) of 37% formalin, and the mixture was allowed to react at 70C for 4 hours. After adjusting to pH 4.0 with 70% sulfuric acid, the reaction mixture was further allowed to react at 70C for 4 hours. The reaction mixture was adjusted to pH 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R2 having a resin content of 60% and a vi.scosity of 230 cps.
In the same apparatus as used in Reference Example l were charged 103.2 g (1.0 mol) of diethylenetriamine and 120.1 g (2.0 mol) of urea, and the mixture was heated at an inner temperature of 120 - 140C for 2 hours to remove ammonia.
Then, 33.6 g of water was added thereto to prepare an aqueous resin solution. To the solution was added 81.2 g (1.0 mol) of 37~ formalin, and the mixture was allowed to react at 70C
for 4 hours. After adjusting to pH 4.0 with 70~ sulfuric acid, the reaction mixture was further allowed to react at 70C for 4 hours. The reaction mixture was adjusted to pH
CH-Y
CH2- z wherein X represents a halogen atom, and either one of Y and Z represents a halogen atom and the other represents a hydroxyl group.
Preferred examples thereof include 1,3-dichloro-2-propanol and 2,3-dichloro-l~propanol.
Particularly preferred of these quaternarization agents is epichlorohydrin. The quaternarization a~ents may be used either individually or in combination of two or more thereof.
Polyamine (B) may be either one or both of polyalXylene-polyamine (c) and reaction product (d) between polyalkylene-polyamine (c) and the quaternarization agent.
- 17 ~
-` h~ ? ~L ~
Pigments which can be used as component (I) in the present invention include white inoxganic pigments, e.g., kaolin, talc, calcium carbonate (either ground or precipitated), aluminum hydroxide, satin whit~ and titanium oxide; and white organic synthetic pigments, e.g., polystyrene, melamine-formaldehyde resins, and urea-formaldehyde resins. They may be used either individually or in combination of two or more thereof. Organic or inorganic colored pigments may ~lso be used in combination.
Aqueous binders which can be used in the present invention as component (II) includes water-soluble binders and aqueous emulsion type binders. Examples of the water-soluble binders include modified or unmodified starches such as oxidized starch and phosphate-esterified starch, polyvinyl alcohol, water-soluble proteins such as casein and gelatin, and modifled cellulose such as carboxymethyl-cellulose.
Examples of the aqueous emulsion type binders include styrene-butadiene type resins, vinyl acetate xesins, ethylene-vinyl acetate resins, and methyl methacrylate-based resins. These aqueous binders may be used either ind;vidually or in combination of two or more thereof.
In the paper coating composition according to the present invention, resinous ingredient (III) is used preferably in an amount of from 0.05 to 5 parts by weight, more preferably from 0.1 to 2 parts by weight, per 100 parts by weight of pigment (I). The amount of resinous ingredient (III) ~ 18 ~
referred to herein is applicable to any of cases where the resinous ingredient (III) comprises water-soluble resin (A) alone, where it comprises both water-soluble resin (~) and polyamine (B), and where it comprises reaction product (C) prepared by further reacting water-soluble resin (A) with polyamine (B).
Aqueous binder (II) per se is conventionally used as a component for paper coating compositions, and its amount in the composition can vary in accordance with the usage of the composition. Aqueous binder (II) contained in the paper coating composition of the present invention is preferably in an amount of from 5 to 200 parts by weight, more preferably from 10 to 50 parts by weight, per 100 parts by weight of pigment (I).
The paper coating composition of the present invention preferably has a solids content ranging from about 20 to about 75% by weight based on the weight of the composition, but the solid content can vary depending on the kind of a coater, the usage of the composition and the like.
In the prepaxation of the paper coating composi.tion of the present invention, while resinous ingredient (III) is usually admixed ~ith the pigment and aqueous binder at the preparation of the composition, the effects of the present invention can be achieved as well by previously admixing resinous ingredient (III~ with either a piyment slurry or an ~,J ~ r., aqueous binder and then incorporating the mixture with other components.
If desired, the paper coating composition of the present invention may further contain other components, such as dispersing agents, viscosity or fluidity regulators, defoaming agents, antiseptics, lubricants, water retaining agents, and colorants including dyes and colored pigments.
The paper coating composition of the present invention can be applied on a paper su~strate by any of known coating means, such as blade coater, air knife coater, bar coater, size press coater, gate roll coater, and cast coater After coating, the paper is subjected to drying as required. If desired, the coated paper is subjected to a surface smoothening treatment by use of a supercalender, etc.
Coated paper obtained by using the paper coating composition according to the present invention exhibits various excellent properties. For example, it is excellent in ink receptivity and water resistance, and is particularly excellent in anti-blister property. Further, it is completely or substantially free from evolution of formaldehyde odor.
The present invention is now illustrated in greater detail with reference to Reference Examples and Examples, but it should be understood that the present invention is not deemed to be limited thereto. All the percents, parts and ratios are ~y weight unless otherwise indicated. In the _ 20 ~
3 ~, ~
Reference Examples and Examples, viscosities ~ere measured at 25C.
REFERENCE EX~MPLE 1 In a four-necked flask equipped with a thermometer, a reflux condens~r, and a stirring rod were charged 146.2 g (1.0 mol) of triethylenetetramine and 180.2 g ~3.0 mol) of urea, and the mixture was heated at an inner temperature of 120 - 140C for 2 hours to effect deammoniation. Thereafter, 150.4 g of water was added thereto to prepare an aqueous resin solution. To the solution was added 56.8 g (0.7 mol) of 37% formalin, and the mixture was allowed to react at 70C
for 4 hours. The reaction system was adjusted to pH 4.0 with 70% sulfuric acid, and the reaction was further continued at 70C for an additional period of 4 hours. The reaction mixture was adjusted to pH 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution Rl having a resin content of 60% and a viscosity of 350 cps.
In the same apparatus as used in Reference Example 1 were charged 146.2 g (1.0 mol) of triethylenetetramine and 60.1 g tl.0 mol) of urea, and the mixture was heated at an inner temperature of 140 - 160C for 3 hours to effect deammoniation. After cooling to 120C, 120.1 g (2.0 mol) of urea was added to the reaction mixture, followed by heating at an inner temperature of 120 - 130C for 2 hours to conduct deammoniation. Then, 134.9 g of water was added thereto to prepare an aqueous resin solution. To the solution was added 81.2 g ~1.0 mol) of 37% formalin, and the mixture was allowed to react at 70C for 4 hours. After adjusting to pH 4.0 with 70% sulfuric acid, the reaction mixture was further allowed to react at 70C for 4 hours. The reaction mixture was adjusted to pH 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R2 having a resin content of 60% and a vi.scosity of 230 cps.
In the same apparatus as used in Reference Example l were charged 103.2 g (1.0 mol) of diethylenetriamine and 120.1 g (2.0 mol) of urea, and the mixture was heated at an inner temperature of 120 - 140C for 2 hours to remove ammonia.
Then, 33.6 g of water was added thereto to prepare an aqueous resin solution. To the solution was added 81.2 g (1.0 mol) of 37~ formalin, and the mixture was allowed to react at 70C
for 4 hours. After adjusting to pH 4.0 with 70~ sulfuric acid, the reaction mixture was further allowed to react at 70C for 4 hours. The reaction mixture was adjusted to pH
7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R3 having a resin content of 60% and a viscosity of 540 cps.
REFERENCE EX~MPLE 4 Deammoniation reaction was conducted in the same manner as in Reference Example 1. To the resulting reaction mixture was added 215.4 g of water, and 64.8 g (0.7 mol) of epichlorohydrin was further added thereto. The mixture was allowed to react at 70C for 4 hours to obt~in an aqueous water-soluble resin solution R4 having a resin content of 60%, a viscosity of 300 cps and a pH of 6.2.
To 465.S g of an aqueous water-soluble resin solution obtained in the same manner as in Reference Example 1 were added 14.6 g (0.1 mol) of triethylenetetramine and 9.1 g of water to obtain an aqueous water-soluble resin solution R5 having a resin content of 60%, a viscosity of 340 cps and a pH of 8Ø
In the same apparatus as used in Reference Example 1 were charged 43.9 g (0.3 mol) of triethylenetetramine and 140.3 g of water, and 166.6 g (1.8 mol) of epichlorohydrin was further added thereto dropwise while keeping the inner temperature at 50C or lower. To the reac~ion mixture was added 465.5 g of an aqueous water-soluble resin solution obtained in the same manner as in Reference Example 1, followed by allowing the mixture to react at 50C for 1 hour to prepare an aqueous water-soluble resin solution R6 having - ~3 -a resin content of 60%, a viscosity of 300 cps and a pH of 6~5.
In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirring rod were charged 146.2 g (1.0 mol) of triethylenetetramine and 30.0 g (0.5 mol) of urea, and the mixture was heated at an inner temperature of 140 - 160C for 3.5 hours to conduct deammoniation.
Thereafter, 73.1 g ~0.5 mol) of adipic acid was added thereto to conduct deamidation at 150 - 160C for 5 hours. After cooling to 130C, 120.1 g (2.0 mol) of urea was added to the reaction mixture, and ammonia was removed at 120 - 130C for 2 hours. Then, 284.5 g of water was added thereto to prepare an aqueous resin solution. To the solution was added 60.9 g (0.75 mol) of 37% formalin, and the system was adjusted to a pH of 4 - 5 with 70% sulfuric acid, followed by allowing the mixture to react at an inner temperature of 70C for 4 hours.
The pH of the reaction mixture was adjusted to 6.5 with an aqueous sodium hydroxide solution to obtain an aqueous resin solution CR1 having a resin content of 50% and a viscosity of 140 cps.
~ 24 -G ~
The same procedures as in Reference Example 1 were repeated, except for changing the amounts of urea and water charged to 90.1 g (1.5 mol) and 101.7 g, respectively, to obtain an aqueous resin solution CR2 having a resin content of 60%, a viscosity of 200 cps and a pH of 7Ø
The same procedures as in Reference Example 1 were repeated, except for changing the amounts of urea and water charged to 300.3 g (5 mol) and 230.5 g, respectively, to obtain an aqueous resin solution.CR3 having a resin content of 60%, a viscosity of 150 cps and a pH of 7Ø
The same procedures as in Reference Example 1 were repeated, except that the reaction after the addition of sulfuric acid was not conducted. There was obtained an aqueous resin solution CR4 having a resin content of 60%, a viscosity of 60 cps and a pH of 8.5.
COMPARATIVE REFRRENCE EXAMPLE S
The same procedures as in Reference Example 1 were repeated, except for changing the amounts of 37% formalin and water charged to 73.0 g (0.9 mol) and 144.2 g, respectively, to obtain an aqueous resin solution CR5 havin~ a resin content of 60%, a viscosity of 1,600 cps and a pH of 7Ø
Reactions were conducted in the same manner as in Reference Example 1. The resulting reaction mixture was adjusted to pH 4.0 with 70% sulfuric acid to obtain an aqueous resin solution CR6 having a resin content of 60% and a viscosity of 350 cps.
Reactions were conducted in the same manner as in Reference Example 1. The resulting reaction mixture was tried to be adjusted to pH 11 with an aqueous sodium hydroxide solution. However, a .precipitate was formed in quantity, and a satisfactory aqueous resin solution was not obtained.
A paper coating composition having the following formulation (solid base) was prepared by using each of the aqueous water-soluble resin solutions R1 to R6 and CR1 to CR6 prepared in Reference Examples 1 to 6 and Comparative Reference Examples 1 to 6. The coating compositions using any of the resin solutions CR2, CR5 and CR6 prepared in Comparative Reference Examples 2, 5, and 6 had a too high viscosity to conduct a coating test hereinafter described.
Paper Coatinq ComPosition:
Pigment: Ultrawhite gol) 70 parts Carbital 902~ 30 parts Dispersing Agent:
Sumirez Resin DS-103~ 0.2 part Aqueous Binder: SN-3074) 12 parts Oji Ace A5) 4 parts Water-soluble Thermosetting Resin:
Aqueous resin solution0.5 parts obtained in Reference Example or Comparative Reference Example Note~ Clay produced by Engel Hard Minerals and Chemical Division Inc., U.S.A.
2): Calcium carbonate produced by Fuji Kaolin Co., Ltd., Japan 3): Polyacrylic acid type pigment dispersant produced by Sumitomo Chemical Co., Ltd., Japan 4): Styrene-butadiene latex produced by Sumitomo Naugatuck Co., Ltd., Japan 5): Oxidized starch produced by Oji National Co., Ltd., Japan The paper coating composition was adjusted so as to have a total solids content of 60% and a pH of about 9.0 by addition of water and an aqueous 10% sodium hydroxide solution. The thus prepared composition was applied using a wire rod on one or both sides of fine paper having a basis weight of 80 g/m2 at a single spread of 14 g/m2. The paper was immediately subjected to drying in hot air at 120C for 30 seconds, then to moisture-conditioning at 20C under a relative humidity of 65% for 16 hours, and thereafter to - 27 ~-supercalendering twice at 60C and under a linear pressure of 60 kg/cm to obtain coated paper.
Water resistance, ink receptivity, and anti-blister property of the resulting coated paper were evaluated in accordance with the following test methods. The results obtained are shown in Table 1 below.
Water Resistance:
1-a) Wet Rub Method (WR):
About 0.1 m~ of ion-exchange water was dropped on the coated surface, and 7 rubs with a finger tip were given. The matter rubbed off was transferred to black paper, and its amount was visually observed to evaluate water resistance according to five ratings of from 1 (poor) to 5 texcellent).
1-b) Wet Pick Method (WP):
The coated surface was wetted with a water-supply roll and printed by means of an RI tester (manufactured by Akira Seisakusho Co., Ltd.). Tha picking was visually observed to evaluate water resistance according to five ratings of from 1 (poor) to 5 texce}lent).
2) Ink RecePtivitY:
2-a) Method A:
The coated surface was wetted with a water-supply roll and printed by means of the RI tester. Ink receptivity was visually evaluated according to five ratings of from 1 (poor) to 5 (excellent).
2-b) Method B:
~ t~
Pxinting was carried out while incorporating water into ink by means of the IR tester. Ink receptivity was visually evaluated according to ive ratings of from 1 tpoor) to 5 (excellent).
3 ! Anti-blister _roperty:
Both sides of double-coated paper were printed with offset rotary pressing ink by means of the RI tester. After moisture-conditioning, the printed paper was soaked in a heated silicone oil bath, and the amount of blisters was visually evaluated according to five ratings of from 1 (poor) to S (excellent).
`I O O O O O
~d ~
n x O
a~ o u~ ,, ~ ~ co O
x ~: o u I
O
. I ~ ~ ~ ~ ~ ~ ~ ~ O
u~ . .
I IY; I
7 ~1 O
I r- o ~ ~ ~ ~ O O ~ O O
~ O
æ
~D O
~, ~ o o~
X O
z;
., O co l- ~ ~ ~D CO
~: o ~ O~
æ
~ .C ~Zj ~ o~ ~O ~, d~ d' ';t' d' ' a~ ~ o H PC O rl ~ ~ ~ ~ ~D u~ -~Z
~ O
N . . ' -~; o 1~Cl~ `- d' ~ `':Y ~ ~r Z ~1 ' .
~1 o o o ~ ~ ~ u~
~ 'I . ~o . . . .
1~ 0 1.4O~ ` d' d~ ~ d' . I
I
rJ U V :~
I o . I Ln I
o ~ .. u~
C ~ ~1 0 0 ~ ~ m ~ a) U~ C4 U~
I u ~ cL a I o -1 ~ ~ o o InU~ P~
t t: N 0 ^ ~ h ~ ~ I a~
~: ~ V ~n ~1 O Er~
. I ~ ~;~ ~ ~ X ~ ~ O
I a) ~ V ~ ~ ~ ~ Sl O ~Y; CLI > ~ o~: H ~ C 4 U
hJ ~
To a four-necked flask equipped with a thermometer, a reflux condenser, and a stirring rod were charged 146.2 g (1.0 mol~ of triethylenetetramine and 180.2 g (3.0 mol) of urea, and the mixture was heated at an inner temperature of 120 - 140C for 2 hours to conduct deammoniation. Then, 156.1 g of water was added to prepare an aqueous resin solution. A resin solution separately prepared from 12.0 g (0.2 mol) of urea and 72.5 g (0.5 mol) of an aqueous 40%
glyoxal solution was added to the above prepared aqueous resin solution, and the pH was adjusted to 4.0 with 70%
sulfuric acid, followed by allowing the mixture to react at 70C for 4 hours. Thereafter, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R7 having a resin content of 60% and a viscosity of 75 cps.
To 499.0 g of an aqueous water-soluble resin solution prepared in the same manner as in Reference Example 7 was added 40.6 g (0.5 mol) of 37% formalin, and the pH was adjusted to 4.0 with 70% sulfuric acid, followed by allowing the mixture to react at 70C for 4 hours. Thereafter, the pH
was adjusted to 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R8 having a resin content of 60% and a viscosity of 300 cps.
REFERENCE E~AMPLE 9 To 499.0 g of an aqueous water-soluble resin solution prepared in the same manner as in Reference Example 7 were added 46.3 a (0.5 mol) of epichlorohydrin and 30.9 g of water, and the pH was adjusted to 8.0 with an aqueous sodium hydroxide solution, followed by allowing the mixture to react at 70C for 4 hours to obtain an aqueous water-soluble resin solution R9 having a resin content of 60%, a viscosity of 290 cps and a pH of 6.6.
To 499.0 g of an aqueous water-soluble resin solution prepared in the same manner as in Reference Example 7 were added 14.6 g (0.1 mol) of triethylenetetramine and 9.1 g of water to obtain an aqueous water-soluble resin solution R10 having a resin content of 60~, a viscoslty of 340 cps and a p~ of 8Ø
. .
In the same apparatus as used in Reference Example 7 were charged 43.9 g (0.3 mol) of triethylenetetramine and 140.3 g of water, and 166.6 g (1.8 mol) of epichlorohydrin was further added thereto dropwise while keeping the inner temperature at 50C or lower. To the reaction mixture was added 499.0 g of an aqueous resin solution prepared in the same manner as in Reference Example 7, and the resulting mixture was allowed to react at 50C for 1 hour to obtain an J J,i,. y~ ~l aqueous water-soluble resin solu~ion Rll having a resin content of 60%, a viscosity of 300 cps and a pH of 6.5.
A paper coating composition was prepared in the same manner as in Example 1, except for using each of the resin solutions R7 to Rll prepared in Reference Examples 7 to 11.
Each of the resulting compositions was evaluated in the same manner as in Example 1. The results obtained are shown in Table 2 below.
Xl ~ I a),,~, ~, O O O O O
o o o t~ o c~
~; o l o~r~ ` d' ~r ~ d' d' ~1 ` ~ r,~
1:~ 0 1`
Z ~1 o ~ o j 2 ,~ ~ ~ ~r ~ ~r d' H
I O ~ O ~ ~ ~
~ ~ ~r ~r d' ~14 d' ~:; z~
U~
U
..
.. 0 U U ~, . I In O _ ., rn ~ h ~ ~ ,~ o o ,~
o u ~ c U o .~ 0 .. 1: ~ U ~c~ ~ h ..
a) ~: "
O tr;
C~
) lJ
In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirring rod were charged 146.2 g (1.0 mol) of triethylenetetramine and 180.2 g (3.0 mol) of urea, and the mixture was heated at an inner temperature of 120 - 140C for 2 hours to perform deammoniation. To the mixture was added 191.1 g of water to prepare an aqueous resin solution. To the solution was added 75.8 g (0.25 mol) of an aqueous 75% melamine resin solution prepared by using 3.3 mol of formaldehyde per mol of melamine, and the pH of the mixture was adjusted to 4.0 with 70% sulfuric acid, followed by allowing the mixture to react at 70C for 4 hours. The reaction mixture was adjusted to pH 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R12 having a resin content of 60% and a viscosity of 340 cps.
To 525.2 g of an aqueous resin solution prepared in the same manner as in Reference Example 12 were added 14.6 g (0.1 mol) of triethylenetetramine and 9.1 g of water to prepare an aqueous water-soluble resin solution R13 having a resin content of 60%, a viscosity of 330 cps and a pH of a . o .
To the same apparatus as used in Reference Example 12 were added 43.9 g (0.3 mol) of triethylenetetramine and 140.3 g of water, and 166.6 g (1.8 mol) of epichlorohydrin 3 ~' ~ 5' ~
was futher added thereto dropwise while keeping the inner temperature at 50C or lower. To the mixture was added 525.2 g of an aqueous resin solution prapared in the same manner as in Reference Example 12, followed by allowing the resulting mixture to .react at 50C for 1 hour to prepare an aqueous water-soluble resin solution R14 having a resin content of 60%, a viscosity of 300 cps and a pH of 6.5.
A paper coating composition was prepared in the same manner as in Example 1, except for using each of the resin solutions R12 to R14 prepared in Reference Examples 12 to 14.
Each of the resulting composition was evaluated in the same manner as in Example 1. The results obtained are shown in Table 3 below.
Compa-Invention rison Blank Run Run Run Run Run No. 1 No. 2 No. 3 No. 4 No. 5 Coatinq_~mposition:
Resin R12 R13 R14 CRlnone pH ~25C) 9.1 9.1 9.0 9.1 9.2 Viscosity ~25C) (cps)1,630 1,690 1,7601,600 1,620 Coated Paper.
Water resistance:
WR method 4.3 4.1 4.2 3.0 1.0 WP method 4.3 4.3 4.3 3.0 1.0 Ink receptivity:
Method A 4.2 4.3 4.4 3.2 l.0 Method B 4.1 4.7 4.7 3.0 1.0 Anti~blister property 4.5 4.6 4.7 3.0 l.0 While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
REFERENCE EX~MPLE 4 Deammoniation reaction was conducted in the same manner as in Reference Example 1. To the resulting reaction mixture was added 215.4 g of water, and 64.8 g (0.7 mol) of epichlorohydrin was further added thereto. The mixture was allowed to react at 70C for 4 hours to obt~in an aqueous water-soluble resin solution R4 having a resin content of 60%, a viscosity of 300 cps and a pH of 6.2.
To 465.S g of an aqueous water-soluble resin solution obtained in the same manner as in Reference Example 1 were added 14.6 g (0.1 mol) of triethylenetetramine and 9.1 g of water to obtain an aqueous water-soluble resin solution R5 having a resin content of 60%, a viscosity of 340 cps and a pH of 8Ø
In the same apparatus as used in Reference Example 1 were charged 43.9 g (0.3 mol) of triethylenetetramine and 140.3 g of water, and 166.6 g (1.8 mol) of epichlorohydrin was further added thereto dropwise while keeping the inner temperature at 50C or lower. To the reac~ion mixture was added 465.5 g of an aqueous water-soluble resin solution obtained in the same manner as in Reference Example 1, followed by allowing the mixture to react at 50C for 1 hour to prepare an aqueous water-soluble resin solution R6 having - ~3 -a resin content of 60%, a viscosity of 300 cps and a pH of 6~5.
In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirring rod were charged 146.2 g (1.0 mol) of triethylenetetramine and 30.0 g (0.5 mol) of urea, and the mixture was heated at an inner temperature of 140 - 160C for 3.5 hours to conduct deammoniation.
Thereafter, 73.1 g ~0.5 mol) of adipic acid was added thereto to conduct deamidation at 150 - 160C for 5 hours. After cooling to 130C, 120.1 g (2.0 mol) of urea was added to the reaction mixture, and ammonia was removed at 120 - 130C for 2 hours. Then, 284.5 g of water was added thereto to prepare an aqueous resin solution. To the solution was added 60.9 g (0.75 mol) of 37% formalin, and the system was adjusted to a pH of 4 - 5 with 70% sulfuric acid, followed by allowing the mixture to react at an inner temperature of 70C for 4 hours.
The pH of the reaction mixture was adjusted to 6.5 with an aqueous sodium hydroxide solution to obtain an aqueous resin solution CR1 having a resin content of 50% and a viscosity of 140 cps.
~ 24 -G ~
The same procedures as in Reference Example 1 were repeated, except for changing the amounts of urea and water charged to 90.1 g (1.5 mol) and 101.7 g, respectively, to obtain an aqueous resin solution CR2 having a resin content of 60%, a viscosity of 200 cps and a pH of 7Ø
The same procedures as in Reference Example 1 were repeated, except for changing the amounts of urea and water charged to 300.3 g (5 mol) and 230.5 g, respectively, to obtain an aqueous resin solution.CR3 having a resin content of 60%, a viscosity of 150 cps and a pH of 7Ø
The same procedures as in Reference Example 1 were repeated, except that the reaction after the addition of sulfuric acid was not conducted. There was obtained an aqueous resin solution CR4 having a resin content of 60%, a viscosity of 60 cps and a pH of 8.5.
COMPARATIVE REFRRENCE EXAMPLE S
The same procedures as in Reference Example 1 were repeated, except for changing the amounts of 37% formalin and water charged to 73.0 g (0.9 mol) and 144.2 g, respectively, to obtain an aqueous resin solution CR5 havin~ a resin content of 60%, a viscosity of 1,600 cps and a pH of 7Ø
Reactions were conducted in the same manner as in Reference Example 1. The resulting reaction mixture was adjusted to pH 4.0 with 70% sulfuric acid to obtain an aqueous resin solution CR6 having a resin content of 60% and a viscosity of 350 cps.
Reactions were conducted in the same manner as in Reference Example 1. The resulting reaction mixture was tried to be adjusted to pH 11 with an aqueous sodium hydroxide solution. However, a .precipitate was formed in quantity, and a satisfactory aqueous resin solution was not obtained.
A paper coating composition having the following formulation (solid base) was prepared by using each of the aqueous water-soluble resin solutions R1 to R6 and CR1 to CR6 prepared in Reference Examples 1 to 6 and Comparative Reference Examples 1 to 6. The coating compositions using any of the resin solutions CR2, CR5 and CR6 prepared in Comparative Reference Examples 2, 5, and 6 had a too high viscosity to conduct a coating test hereinafter described.
Paper Coatinq ComPosition:
Pigment: Ultrawhite gol) 70 parts Carbital 902~ 30 parts Dispersing Agent:
Sumirez Resin DS-103~ 0.2 part Aqueous Binder: SN-3074) 12 parts Oji Ace A5) 4 parts Water-soluble Thermosetting Resin:
Aqueous resin solution0.5 parts obtained in Reference Example or Comparative Reference Example Note~ Clay produced by Engel Hard Minerals and Chemical Division Inc., U.S.A.
2): Calcium carbonate produced by Fuji Kaolin Co., Ltd., Japan 3): Polyacrylic acid type pigment dispersant produced by Sumitomo Chemical Co., Ltd., Japan 4): Styrene-butadiene latex produced by Sumitomo Naugatuck Co., Ltd., Japan 5): Oxidized starch produced by Oji National Co., Ltd., Japan The paper coating composition was adjusted so as to have a total solids content of 60% and a pH of about 9.0 by addition of water and an aqueous 10% sodium hydroxide solution. The thus prepared composition was applied using a wire rod on one or both sides of fine paper having a basis weight of 80 g/m2 at a single spread of 14 g/m2. The paper was immediately subjected to drying in hot air at 120C for 30 seconds, then to moisture-conditioning at 20C under a relative humidity of 65% for 16 hours, and thereafter to - 27 ~-supercalendering twice at 60C and under a linear pressure of 60 kg/cm to obtain coated paper.
Water resistance, ink receptivity, and anti-blister property of the resulting coated paper were evaluated in accordance with the following test methods. The results obtained are shown in Table 1 below.
Water Resistance:
1-a) Wet Rub Method (WR):
About 0.1 m~ of ion-exchange water was dropped on the coated surface, and 7 rubs with a finger tip were given. The matter rubbed off was transferred to black paper, and its amount was visually observed to evaluate water resistance according to five ratings of from 1 (poor) to 5 texcellent).
1-b) Wet Pick Method (WP):
The coated surface was wetted with a water-supply roll and printed by means of an RI tester (manufactured by Akira Seisakusho Co., Ltd.). Tha picking was visually observed to evaluate water resistance according to five ratings of from 1 (poor) to 5 texce}lent).
2) Ink RecePtivitY:
2-a) Method A:
The coated surface was wetted with a water-supply roll and printed by means of the RI tester. Ink receptivity was visually evaluated according to five ratings of from 1 (poor) to 5 (excellent).
2-b) Method B:
~ t~
Pxinting was carried out while incorporating water into ink by means of the IR tester. Ink receptivity was visually evaluated according to ive ratings of from 1 tpoor) to 5 (excellent).
3 ! Anti-blister _roperty:
Both sides of double-coated paper were printed with offset rotary pressing ink by means of the RI tester. After moisture-conditioning, the printed paper was soaked in a heated silicone oil bath, and the amount of blisters was visually evaluated according to five ratings of from 1 (poor) to S (excellent).
`I O O O O O
~d ~
n x O
a~ o u~ ,, ~ ~ co O
x ~: o u I
O
. I ~ ~ ~ ~ ~ ~ ~ ~ O
u~ . .
I IY; I
7 ~1 O
I r- o ~ ~ ~ ~ O O ~ O O
~ O
æ
~D O
~, ~ o o~
X O
z;
., O co l- ~ ~ ~D CO
~: o ~ O~
æ
~ .C ~Zj ~ o~ ~O ~, d~ d' ';t' d' ' a~ ~ o H PC O rl ~ ~ ~ ~ ~D u~ -~Z
~ O
N . . ' -~; o 1~Cl~ `- d' ~ `':Y ~ ~r Z ~1 ' .
~1 o o o ~ ~ ~ u~
~ 'I . ~o . . . .
1~ 0 1.4O~ ` d' d~ ~ d' . I
I
rJ U V :~
I o . I Ln I
o ~ .. u~
C ~ ~1 0 0 ~ ~ m ~ a) U~ C4 U~
I u ~ cL a I o -1 ~ ~ o o InU~ P~
t t: N 0 ^ ~ h ~ ~ I a~
~: ~ V ~n ~1 O Er~
. I ~ ~;~ ~ ~ X ~ ~ O
I a) ~ V ~ ~ ~ ~ Sl O ~Y; CLI > ~ o~: H ~ C 4 U
hJ ~
To a four-necked flask equipped with a thermometer, a reflux condenser, and a stirring rod were charged 146.2 g (1.0 mol~ of triethylenetetramine and 180.2 g (3.0 mol) of urea, and the mixture was heated at an inner temperature of 120 - 140C for 2 hours to conduct deammoniation. Then, 156.1 g of water was added to prepare an aqueous resin solution. A resin solution separately prepared from 12.0 g (0.2 mol) of urea and 72.5 g (0.5 mol) of an aqueous 40%
glyoxal solution was added to the above prepared aqueous resin solution, and the pH was adjusted to 4.0 with 70%
sulfuric acid, followed by allowing the mixture to react at 70C for 4 hours. Thereafter, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R7 having a resin content of 60% and a viscosity of 75 cps.
To 499.0 g of an aqueous water-soluble resin solution prepared in the same manner as in Reference Example 7 was added 40.6 g (0.5 mol) of 37% formalin, and the pH was adjusted to 4.0 with 70% sulfuric acid, followed by allowing the mixture to react at 70C for 4 hours. Thereafter, the pH
was adjusted to 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R8 having a resin content of 60% and a viscosity of 300 cps.
REFERENCE E~AMPLE 9 To 499.0 g of an aqueous water-soluble resin solution prepared in the same manner as in Reference Example 7 were added 46.3 a (0.5 mol) of epichlorohydrin and 30.9 g of water, and the pH was adjusted to 8.0 with an aqueous sodium hydroxide solution, followed by allowing the mixture to react at 70C for 4 hours to obtain an aqueous water-soluble resin solution R9 having a resin content of 60%, a viscosity of 290 cps and a pH of 6.6.
To 499.0 g of an aqueous water-soluble resin solution prepared in the same manner as in Reference Example 7 were added 14.6 g (0.1 mol) of triethylenetetramine and 9.1 g of water to obtain an aqueous water-soluble resin solution R10 having a resin content of 60~, a viscoslty of 340 cps and a p~ of 8Ø
. .
In the same apparatus as used in Reference Example 7 were charged 43.9 g (0.3 mol) of triethylenetetramine and 140.3 g of water, and 166.6 g (1.8 mol) of epichlorohydrin was further added thereto dropwise while keeping the inner temperature at 50C or lower. To the reaction mixture was added 499.0 g of an aqueous resin solution prepared in the same manner as in Reference Example 7, and the resulting mixture was allowed to react at 50C for 1 hour to obtain an J J,i,. y~ ~l aqueous water-soluble resin solu~ion Rll having a resin content of 60%, a viscosity of 300 cps and a pH of 6.5.
A paper coating composition was prepared in the same manner as in Example 1, except for using each of the resin solutions R7 to Rll prepared in Reference Examples 7 to 11.
Each of the resulting compositions was evaluated in the same manner as in Example 1. The results obtained are shown in Table 2 below.
Xl ~ I a),,~, ~, O O O O O
o o o t~ o c~
~; o l o~r~ ` d' ~r ~ d' d' ~1 ` ~ r,~
1:~ 0 1`
Z ~1 o ~ o j 2 ,~ ~ ~ ~r ~ ~r d' H
I O ~ O ~ ~ ~
~ ~ ~r ~r d' ~14 d' ~:; z~
U~
U
..
.. 0 U U ~, . I In O _ ., rn ~ h ~ ~ ,~ o o ,~
o u ~ c U o .~ 0 .. 1: ~ U ~c~ ~ h ..
a) ~: "
O tr;
C~
) lJ
In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirring rod were charged 146.2 g (1.0 mol) of triethylenetetramine and 180.2 g (3.0 mol) of urea, and the mixture was heated at an inner temperature of 120 - 140C for 2 hours to perform deammoniation. To the mixture was added 191.1 g of water to prepare an aqueous resin solution. To the solution was added 75.8 g (0.25 mol) of an aqueous 75% melamine resin solution prepared by using 3.3 mol of formaldehyde per mol of melamine, and the pH of the mixture was adjusted to 4.0 with 70% sulfuric acid, followed by allowing the mixture to react at 70C for 4 hours. The reaction mixture was adjusted to pH 7.0 with an aqueous sodium hydroxide solution to obtain an aqueous water-soluble resin solution R12 having a resin content of 60% and a viscosity of 340 cps.
To 525.2 g of an aqueous resin solution prepared in the same manner as in Reference Example 12 were added 14.6 g (0.1 mol) of triethylenetetramine and 9.1 g of water to prepare an aqueous water-soluble resin solution R13 having a resin content of 60%, a viscosity of 330 cps and a pH of a . o .
To the same apparatus as used in Reference Example 12 were added 43.9 g (0.3 mol) of triethylenetetramine and 140.3 g of water, and 166.6 g (1.8 mol) of epichlorohydrin 3 ~' ~ 5' ~
was futher added thereto dropwise while keeping the inner temperature at 50C or lower. To the mixture was added 525.2 g of an aqueous resin solution prapared in the same manner as in Reference Example 12, followed by allowing the resulting mixture to .react at 50C for 1 hour to prepare an aqueous water-soluble resin solution R14 having a resin content of 60%, a viscosity of 300 cps and a pH of 6.5.
A paper coating composition was prepared in the same manner as in Example 1, except for using each of the resin solutions R12 to R14 prepared in Reference Examples 12 to 14.
Each of the resulting composition was evaluated in the same manner as in Example 1. The results obtained are shown in Table 3 below.
Compa-Invention rison Blank Run Run Run Run Run No. 1 No. 2 No. 3 No. 4 No. 5 Coatinq_~mposition:
Resin R12 R13 R14 CRlnone pH ~25C) 9.1 9.1 9.0 9.1 9.2 Viscosity ~25C) (cps)1,630 1,690 1,7601,600 1,620 Coated Paper.
Water resistance:
WR method 4.3 4.1 4.2 3.0 1.0 WP method 4.3 4.3 4.3 3.0 1.0 Ink receptivity:
Method A 4.2 4.3 4.4 3.2 l.0 Method B 4.1 4.7 4.7 3.0 1.0 Anti~blister property 4.5 4.6 4.7 3.0 l.0 While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (20)
1. A paper coating composition which comprises:
(I) a pigment, (II) an aqueous binder, and (III) a resinous ingredient comprising (A) a water-soluble resin which is prepared by cross-linking (a) a condensation product of (a1) an alkylenediamine or a polyalkylenepolyamine and (a2) an urea compound with (b) a cross-linking compound.
(I) a pigment, (II) an aqueous binder, and (III) a resinous ingredient comprising (A) a water-soluble resin which is prepared by cross-linking (a) a condensation product of (a1) an alkylenediamine or a polyalkylenepolyamine and (a2) an urea compound with (b) a cross-linking compound.
2. The composition according to claim 1, wherein said alkylenediamine or polyalkylenepolyamine (a1) is selected from the group consisting of diethylenetriamine and triethylenetetramine.
3. The composition according to claim 1, wherein said urea compound (a2) is urea.
4. The composition according to claim 1, wherein said urea compound (a2) is used in an amount of from 0.5 to 1 mol per mol of the primary and secondary amino groups contained in said alkylenediamine or polyalkylenepolyamine (a1).
5. The composition according to claim 1, wherein said cross-linking compound (b) is (b1) an aldehyde, and said resin (A) is prepared under a cross-linking condition of a pH
of 7 or below.
of 7 or below.
6. The composition according to claim 5, wherein said aldehyde (b1) is formaldehyde or glyoxal.
7. The composition according to claim 5, wherein said resin (A) is prepared by the reaction at a pH ranging from 8 to 12, and thereafter at a pH of 7 or below.
8. The composition according to claim 1, wherein said cross-linking compound (b) is (b2) an epihalohydrin or an a,?-dihalo-.beta.-hydrin.
9. The composition according to claim 8, wherein said resin (A) is prepared by the reaction at a pH of 5 or higher.
10. The composition according to claim 1, wherein said cross-linking compound (b) is (b3) a reaction product of (b3-1) an urea compound with (b3-2) glyoxal.
11. The composition according to claim 10, wherein said resin (A) is prepared by the reaction at a pH of 7 or below.
12. The composition according to claim 10, wherein said water-soluble resin (A) prepared from the condensation product (a) and the reaction product (b3) further react with a compound selected from the group consisting of an aldehyde, an epihalohydrin and an a,?-dihalo-.beta.-hydrin.
13. The composition according to claim 1, wherein said cross-linking compound (b) is (b4) a melamine-formaldehyde resin.
14. The composition according to claim 13, wherein said resin (A) is prepared by the reaction at a pH of 7 or below.
15. The composition according to claim 1, wherein the water-soluble resin (A) has a viscosity of from 50 to 1,000 cps at 25°C and a pH of from 6 to 10, each in an aqueous solution of 60% by weight.
16. The composition according to claim 1, wherein said resinous ingredient (III) further comprises (B) a polyamine selected from the group consisting of (c) a polyalkylene-polyamine and (d) a reaction product of a polyalkylenepoly-amine with a quaternarization agent.
17. The composition according to claim 1, wherein said resinous ingredient (III) is (C) a reaction product prepared from the water-soluble resin (A) by further reacting with (B) a polyamine selected from the group consisting of (c) a poly-alkylenepolyamine and (d) a reaction product of a poly-alkylenepolyamine with a quaternarization agent.
18. The composition according to claim 1, wherein said resinous ingredient (III) is present in an amount of from 0.05 to 5 parts by weight per 100 parts by weight of the pigment (I).
19. The composition according to claim 1, wherein said aqueous binder (II) is present in an amount of from 5 to 200 parts by weight per 100 parts by weight of the pigment (I).
20. The composition according to claim 1, which comprises 100 parts by weight of the pigment (I), from 10 to 50 parts by weight of the aqueous binder (II), and from 0.1 to 2 parts by weight of the resinous ingredient (III).
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2213933A JP2979600B2 (en) | 1990-08-10 | 1990-08-10 | Coating composition for paper |
| JP2-213933 | 1990-08-10 | ||
| JP40048190A JP2864738B2 (en) | 1990-12-05 | 1990-12-05 | Coating composition for paper |
| JP2-400481 | 1990-12-05 | ||
| JP40494190A JP2913839B2 (en) | 1990-12-21 | 1990-12-21 | Coating composition for paper |
| JP2-404941 | 1990-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2048186A1 true CA2048186A1 (en) | 1992-02-11 |
Family
ID=27329560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002048186A Abandoned CA2048186A1 (en) | 1990-08-10 | 1991-07-31 | Paper coating composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5131951A (en) |
| EP (1) | EP0471486B1 (en) |
| AU (1) | AU632430B2 (en) |
| CA (1) | CA2048186A1 (en) |
| DE (1) | DE69128222T2 (en) |
| FI (1) | FI106390B (en) |
| NZ (1) | NZ239340A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318624A (en) * | 1992-09-04 | 1994-06-07 | Eastman Kodak Company | Process for preparing a dispersion from an agglomerated mixture |
| US5283129A (en) * | 1992-10-21 | 1994-02-01 | Champion International Corporation | Light weight paper stock |
| DE69415883T2 (en) * | 1993-07-16 | 1999-08-26 | Sumitomo Chemical Co | Paper coating composition |
| DE4335194A1 (en) * | 1993-10-15 | 1995-04-20 | Basf Ag | Aqueous pigment slurries and their use in the manufacture of paper containing fillers |
| JP3351105B2 (en) * | 1994-07-01 | 2002-11-25 | 住友化学工業株式会社 | Coating composition for paper |
| US6197383B1 (en) * | 1998-04-22 | 2001-03-06 | Sri International | Method and composition for coating pre-sized paper with a mixture of a polyacid and a polybase |
| CH694585A5 (en) * | 1999-04-29 | 2005-04-15 | Ip Vitro Vidrio Y Cristal Ltd | Apparatus for aligning glass sheets on a roller conveyor of a Glühkühlofens. |
| US20030152752A1 (en) * | 2001-09-25 | 2003-08-14 | Oji Paper Co., Ltd. | Water-resistant and organic solvent-resistant recording sheet |
| GB0308487D0 (en) * | 2003-04-14 | 2003-05-21 | Ciba Spec Chem Water Treat Ltd | Paper coating compositions |
| GB0308446D0 (en) * | 2003-04-14 | 2003-05-21 | Sentec Ltd | Low-power magnetic flow meter |
| US7618701B2 (en) | 2005-08-01 | 2009-11-17 | Hewlett-Packard Development Company, L.P. | Porous pigment coating |
| US10344115B2 (en) | 2017-05-25 | 2019-07-09 | International Business Machines Corporation | Amine glyoxal resins |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51121041A (en) * | 1975-04-16 | 1976-10-22 | Sumitomo Chem Co Ltd | Paper coating compositions |
| JPS5531837A (en) * | 1978-08-25 | 1980-03-06 | Sumitomo Chem Co Ltd | Preparation of thermosetting resin aqueous solution |
| EP0081994B1 (en) * | 1981-12-11 | 1988-03-09 | Sumitomo Chemical Company, Limited | Preparation of thermosetting resins and of pigmented compositions thereof for coating on paper |
| JPS59137597A (en) * | 1983-01-17 | 1984-08-07 | 住友化学工業株式会社 | Paper coating composition |
| CA1278898C (en) * | 1985-10-28 | 1991-01-08 | Haruo Tanaka | Process for producing resin for paper coating |
-
1991
- 1991-07-31 CA CA002048186A patent/CA2048186A1/en not_active Abandoned
- 1991-08-02 DE DE69128222T patent/DE69128222T2/en not_active Expired - Fee Related
- 1991-08-02 EP EP91307121A patent/EP0471486B1/en not_active Expired - Lifetime
- 1991-08-08 US US07/741,890 patent/US5131951A/en not_active Expired - Fee Related
- 1991-08-09 AU AU81764/91A patent/AU632430B2/en not_active Ceased
- 1991-08-09 FI FI913796A patent/FI106390B/en not_active IP Right Cessation
- 1991-08-09 NZ NZ239340A patent/NZ239340A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE69128222T2 (en) | 1998-03-19 |
| EP0471486A2 (en) | 1992-02-19 |
| AU8176491A (en) | 1992-02-13 |
| FI106390B (en) | 2001-01-31 |
| EP0471486A3 (en) | 1993-06-30 |
| FI913796A0 (en) | 1991-08-09 |
| EP0471486B1 (en) | 1997-11-19 |
| FI913796A (en) | 1992-02-11 |
| AU632430B2 (en) | 1992-12-24 |
| DE69128222D1 (en) | 1998-01-02 |
| US5131951A (en) | 1992-07-21 |
| NZ239340A (en) | 1992-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5034501A (en) | Process for producing resin for paper coating | |
| FI89820B (en) | TILLSATSBELAEGGNING FOER BINDEMEDEL | |
| US5131951A (en) | Paper coating composition | |
| CA1150870A (en) | Process for producing aqueous solution of thermosetting resin | |
| US5849856A (en) | Water soluble resins and application thereof to paper coating | |
| AU676915B2 (en) | Paper coating composition | |
| CA2059216C (en) | Paper coating resin and paper coating composition | |
| US5521240A (en) | Paper coating composition | |
| JP2979600B2 (en) | Coating composition for paper | |
| JP2913839B2 (en) | Coating composition for paper | |
| CA1187226A (en) | Paper coating composition | |
| JP3269221B2 (en) | Paper coating resin and paper coating composition containing the same | |
| JP3821474B2 (en) | Resin composition for paper coating | |
| CA1187225A (en) | Paper coating composition | |
| JP2864738B2 (en) | Coating composition for paper | |
| JP2987996B2 (en) | Manufacturing method of coated paper | |
| JP2946757B2 (en) | Coating composition for paper | |
| JP2913845B2 (en) | Coating composition for paper | |
| JPS62125093A (en) | Paper coating composition | |
| JP2008019520A (en) | Resin composition for paper coating | |
| JPS61252396A (en) | Paper coating composition | |
| JPS62156388A (en) | Paper coating composition | |
| JPS58180695A (en) | Paper coating composition | |
| JPH07119087A (en) | Paper-coating resin and paper-coating composition containing the resin | |
| JPH06166992A (en) | Resin for coating paper and paper-coating composition containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |